Titanate composition



Patented Oct. 10, 1 950 2,525,627 TITANATE COMPOSITION Eugene Wainer, Cleveland Heights, Ohio, as-

signor, by theme assignments, to NationalLead Company, New York, N. Y2, a corporation of New Jersey No Drawing. Original application November 12,

1942, Serial No. 465,387. Divided and'this application July 16, 1948, Serial No. 39,177

The present application, which relates to ceramic materials, is a division of my application Serial No. 465,387 (now Patent No. 2,467,169, April 12, 1949) which was filed on November 12, 1942. The invention described and claimed in the present application comprises ceramic materials in which the major constituents consist of combinations of titanates, one of which is lead titanate.

The use of compounds of titanium in the production of dielectric materials is known but, according to the prior art, it has been generally believed that most desirable electrical characteristics are achieved in the case of compositions having an excess of titanium dioxide. According to the present invention, it is found that manifold higher dielectric constants are attainable by forming ceramic dielectric bodies wherein there is substantially no free titanium dioxide and wherein a mixture of titanates of more than one metal is employed.

In no case can the dielectric characteristics of the ceramic materials of the present invention be approached or approximated by a mixture of a titanate with TlOz, or by a single titanate alone, or by a mixture of titanates plus material quantities of T102. The controlling factors in the formation of the present bodies are the presence of more than one titanate andthe substantial absence of free rutile (T102), in the final product.

The precise reason for the surprising dielectric results attained by mixtures of more than one titanate, as compared with bodies comprising single titanates, is not definitely and certainly known, but it has been found. that peak dielectric constants of various mixtures of titanates are found to occur when the combined titanates have a definite gram-molecular ratio, of which more will appear later herein.

Titanium dioxide ceramic dielectric bodies are a relatively recent development and those thus far known generally have dielectric constants in the neighborhood of 100. Some of the mixtures of titanates prepared in accordance with the present invention have dielectric constants between 3000 and 4000, and dielectric constants of 1000 are commonly encountered.

While various titanates may be mixed interchangeably to produce ceramic dielectric bodies, according to the present invention, compositions of titanates of barium or strontium or combinations thereof with lead titanate, are found toyield surprising results.

The novel compositions of the present invention consist of fired mixtures of prefired titan- 6 Claims. (Cl. 10639) ates prepared by combining chosen lots of the foregoing oxides with titanium dioxide. In all cases, the titanate compositions are not to contain T102 in amounts exceeding 50 gram-molecular (molar) percent. For the various compositions set forth in the ensuing examples, the percentages by weight of TiOz are from 25 to 45 per cent with 30 to 40 per cent by weight of 'IiOz preferred. It is, however, the stated grammolecular percentage which is important because of the desire to produce the titanate substantially free of crystalline rutile and with titanium oxide present only in chemical combination with the other titanate-forming oxide. To further this result, it is better in some cases to have in the batch of mixed titanates, before firing, a slight excess of one of the constituents which react with rutile to form titanates so that the fired batch has definitely les than 50 grammolecular per cent of TiOz.

As examples of the high dielectric ceramic compositions of the foregoing general discussion, reference will now be had to certain groups or lots of mixtures of titanates by way of example, comprisin mixtures Of titanates selected from among barium titanate, strontium titanate, and lead titanate.

Lot I .Mixtures of BaTiOg and PbTiOs, wherein the BaTiOs is in any proportion between 20% and 95%, weight with the PbTiOs varying correspondingly from to 5% by Weight.

Lot II.-Mixtures as in Lot I with up to 10 molar per cent of BaO added to the raw batch before firing.

Lot III.-Mixtures of SrTiOs and PbTiO3, wherein the SrTiOa is in any proportion between 20% and by weight with the PbTiOs varying correspondingly from 80% to 5% by weight.

Lot I V.Mixtures as in Lot III with up to 10 molar per cent of SrO added to the raw batch before firing.

Lot V.Mixtures of SrTiOs, BaTiOa and PbTiOs. In thi group the PbTiOs constituent need not exceed 20% by weight and as low as 2% by weight of the SlTiOs and the BaTiOs may vary with one of the oxides of such alkaline earth combination in any proportion between 5% and 95% by weight and the other oxide Water and are fired to vitrification temperatures by conventional methods. Some of the dielectric bodies of the foregoing groups are subject to cracking while being fired. It has been found that small amounts of borates, borosilicates, or boron titanate avoids this danger and gives the bodies proper firing characteristics Without materially altering the desired electrical properties.

The following tabulations give the electrical characteristics of bodies of the various foregoing group or lot definitions. In each case the materials are mixed as the preferred powder, water is added and the bodies are pressed to shape in steel molds and fired in saggers in an oxidizing atmosphere to the temperatures indicated in the tabulation, such temperature being maintained for three hours.

Examples of Lot I v Dielectric Constant fi Oa PbTlOg, Wt. Per Wt. Per ,gg g

Cent 1 kilo. 1 meg.

F. 11 95 5 2, 400 640 210 12 80 2O 2, 300 1, 430 442 13 5O 5O 2, 300 2, 100 1, 200 14 2O 8O 2, 200 460 240 Examples of Lot II Ba'liOi lPbTiOa, Dielectric 5 Wt. Per Wt. Per Constant, 1 51 Cent I Cent megacyclc 15 60 30 i 10 912 (The above was fired at 2,280 F.)

Examples of Lot III SrTiOs PbTiOs, Dielectric Constant 2 2? Wt. Per Wt. Per s1 1 Cent Cent 1 kilo. 1 meg.

F. 16 95 5 2, 350 310 220 17 90 10 2, 350 323 280 v 18 85 15 2, 350 320 300 j 19 80 20 2, 350 340 310 20 75 2, 300 600 560 21 6O 4O 2, 150 790 804 22 5O 50 2, 150 895 910 23 4O 0 2, 100 742 740 24 70 2, 100 560 510 25 20 80 2, 100 295 280 Examples of Lot IV SrTiOi, PbTlO3 Dielectric .22 Wt. Pcr Wt. Per Constant, 1 $1 Cent Cent megacycle (The above was fired at 2,275 F.)

Examples of Lot V Dielectric Conp Sr P103, BaTl9a, PPTlOs, Firing stant Hon \i t. Per Wt. 1 er \l t. Per Tem Cent Cent Cent a 1 kilo. 1 meg.

F. 27 30 15 5 2, 400 320 320 28 8O 10 10 2, 400 440 390 29 7O 15 15 2, 250 370 302 30 7O 25 5 2, 300 393 380 31 6O 35 5 2, 300 520 508 32 5O 5 2, 260 908. 840

The following is an example of the strontium titanate-lead titanate mixture with boron titanate added to avoid cracking in firing:

SrTiOs, PbTlOa, BzTl'Os, Dielectric Composition Wt. Per Wt. Per Wt. Per Constant, 1

Cent Cent Ccnt megacycle (The above was fired at 2,200 F.)

In addition to the above, a composition comprised of by weight of SITIOs, 10% by weight of PbTiCs and 5% by weight of LazOs was prepared and fired at 2350 F. This body exhibited a dielectric constant of 232 at a frequency of 1 megacycle.

It may be pointed out that peak dielectric constants are attained, in all of the various mixtures set forth in the foregoing examples, when the mixed titanates are present in a definite molar ratio. In the case of the mixtures of Lot III, the peak dielectric constant appears to be attained with a mixture of 83 parts of strontium titanate to 16 parts of lead titanate. This is almost exactly equivalent to a molar ratio of 9 to 1.

The extremely high dielectric constants of the ceramic bodies of the present invention open new fields in the electrical arts for the application of capacitive principles of coupling and energy transmission and transformation generally.

The high capacitance materials aiforded makes possible capacitive coupling between, for instance, a high tension alternating current transmission line and a telephone line. The extremely high dielectric constants of these materials make it possible to substitute capacitors where resistance connections would otherwise be employed. Application of the materials disclosed herein in the fields of pyroelectricity and Supersonics is indicated and its use in the construction of crystal or condenser microphones, frequency stabilizers, amplifiers, phonograph pickups and oscillators generally will be found highly advantageous. Some of the members of the foregoing groups exhibit the electrical and mechanical characteristics of piezo electric and pyroelectric crystals.

The very high dielectric constant of these materials provides an effective substitute for clear block condenser mica as used in radio and communication work. These bodies may also be used as substitutes for paper and electrolytic condensers for use in filter and by-pass circuits. They may also be used as power factor control condensersg'fo'r A. C. induction motors, as high voltage capacitors, in television, as starting devices for single phase motors, for elimination of sparking at contact points, and in analogous dielectric applications.

Whil specific-examples of the dielectric material of the present invention are set forth by way of:illustration, it is to be understood that the present invention is not to be considered limited'thereto or otherwise than as defined in the appended claims.

What is claimed is:

1. A range of ceramic compositions comprising as essential constituents by weight a combination of 5 to 80 per cent of lead titanate and to 20 per cent of titanate chosen from the group consisting of barium and strontium titanate, said composition containing about 25 to 45 per cent of combined titanium dioxide.

2. A range of ceramic compositions comprising as essential constituents by weight a combination of 5 to 80 per cent of lead titanate and 95 to 20 per cent of barium titanate, said composition containing substantially solely titanium dioxide which is chemically combined with oxide constituents as titanate.

3. A range of ceramic compositions comprising as essential constituents by weight a combination of 5 to 80 per cent of lead titanate and 95 to 20 per cent of strontium titanate, said composition containing substantially solely titanium dioxide which is chemically combined with oxide constituents as titanate.

4. A range of vitrified ceramic compositions consisting essentially of a combination by weight of 5 to 80 per cent of lead titanate and 95 to 20 per cent of titanate chosen from the group consisting of titanate chosen from the group consisting of barium and strontium titanate, said combination having admixed therewith an excess up to molar per cent of oxide chosen from the group of barium and strontium oxides, the proportion of combined titanium dioxide in said compositions being within the range of 35 to 40 per cent.

5. A dielectric composition comprising a combination of lead titanate and barium titanate and in admixture therewith an excess up to 10 molar per cent of barium oxide, the titanates in said combination bearing complementary proportions with respect to another within a range of 80 to 5 per cent of lead titanate and to 95 per cent of barium titanate, the proportion of combined titanium dioxide in said composition being within the range of to per cent.

6. A dielectric body comprising as essential ingredients strontium titanate and lead titanate in substantially a molar ratio of 9 to 1, said composition containing by weight about 25" to per cent of titanium dioxide which is wholly combined with oxide ingredients as titanate.

EUGENE WAINER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,369,327 Warner Feb. 13, 1945 

1. A RANGE OF CERAMIC COMPOSITIONS COMPRISING AS ESSENTIAL CONSTITUENTS BY WEIGHT A COMBINATION OF 5 TO 80 PER CENT OF LEAD TITANATE AND 95 TO 20 PERCENT OF TITANATE CHOSEN FROM THE GROUP CONSISTING OF BARIUM AND STRONTIUM TITANATE, SAID COMPOSITION CONTAINING ABOUT 25 TO 45 PER CENT OF COMBINED TITANIUM DIOXIDE. 